Catalytic water treatment method and apparatus

ABSTRACT

The present invention relates to methods, apparatuses, and systems for treating water. The methods, apparatuses and systems reduce solubilized water hardness using various water treatment agents bound to a supporting material. The present invention also includes methods of employing treated water, for example, in cleaning or food processing applications.

RELATED APPLICATIONS

This application claims priority to and is related to U.S. ProvisionalApplication Ser. No. 61/171,145 filed on Apr. 21, 2009 and entitled“Catalytic Water Treatment Method and Apparatus.” The entire contents ofthis patent application are hereby expressly incorporated herein byreference including, without limitation, the specification, claims, andabstract, as well as any figures, tables, or drawings thereof.

This application also claims priority and is related to U.S. ProvisionalApplication Ser. No. 61/261,610 filed on Nov. 16, 2009 and entitled“Methods and Apparatus for Controlling Water Hardness.” The entirecontents of this patent application are hereby expressly incorporatedherein by reference including, without limitation, the specification,claims, and abstract, as well as any figures, tables, or drawingsthereof.

This application is also related to U.S. application Ser. No. ______(Attorney Docket No. 2699USU1) filed concurrently herewith and entitled“Methods and Apparatus for Controlling Water Hardness.” The entirecontents of this patent application are hereby expressly incorporatedherein by reference including, without limitation, the specification,claims, and abstract, as well as any figures, tables, or drawingsthereof.

FIELD

The present invention relates to methods and devices for treating anaqueous system, i.e., a water source or stream. In particular, thepresent invention provides methods and devices for reducing solubilizedwater hardness using various water treatment agents bound to asupporting material. Methods for inhibiting or reducing scale formationare also provided. The present invention also relates to methods ofemploying treated water, for example, in cleaning processes.

BACKGROUND

The level of hardness in water can have a deleterious effect in manysystems. For example, when hard water alone, or in conjunction withcleaning compositions, contacts a surface, it can cause precipitation ofhard water scale on the contacted surface. In general, hard water refersto water having a total level of calcium and magnesium ions in excess ofabout 100 ppm expressed in units of ppm calcium carbonate. Often, themolar ratio of calcium to magnesium in hard water is about 2:1 or about3:2. Although most locations have hard water, water hardness tends tovary from one location to another.

Water hardness has been addressed in a number of ways. One methodcurrently used to soften water is via ion exchange, e.g., by exchangingthe calcium and magnesium ions in the water with sodium associated witha resin bed in a water softening unit. The calcium and magnesium adhereto a resin in the softener. When the resin becomes saturated it isnecessary to regenerate it using large amounts of sodium chloridedissolved in water. The sodium displaces the calcium and magnesium,which is flushed out in a briny solution along with the chloride fromthe added sodium chloride. When water softeners regenerate they producea waste stream that contains significant amounts of chloride, and saltsincluding sodium, calcium and magnesium salts, creating a burden on thesystem, e.g., sewer system, in which they are disposed of, including amultitude of downstream water re-use applications like potable waterusages and agriculture. Further, traditional water softeners add to thesalt content in discharge surface waters, which has become anenvironmental issue in certain locations. Therefore a method to handlewater hardness without the use of large amounts of sodium chloride isneeded.

Hard water is also known to reduce the efficacy of detergents, forexample, by forming films on surfaces, and reacting with detergentcomponents making the detergent less functional in the cleaning process.One method for counteracting this includes adding chelating agents orsequestrants into detersive compositions that are intended to be mixedwith hard water in an amount sufficient to handle the hardness. Inseveral instances, chelators and sequestrants (e.g., phosphates and NTA)have been found to cause environmental or health issues. However, inmany instances the water hardness exceeds the chelating capacity of thecomposition. As a result, free calcium ions may be available to attackactive components of the composition, to cause corrosion orprecipitation, or to cause other deleterious effects, such as poorcleaning effectiveness or lime scale build up.

SUMMARY

In some aspects, the present invention provides an apparatus fortreating water. The apparatus includes: an inlet for providing the watersource to a treatment reservoir. One or more catalysts are positionedinside the treatment reservoir. The catalysts comprise a water treatmentagent bound to a supporting material. The water treatment agent isselected from the group consisting of a source of magnesium ions,aluminum ions, zinc ions, titanium ions and mixtures thereof. Theapparatus also includes an outlet for providing treated water from thereservoir.

In some embodiments, the apparatus is located in a washing system. Forexample, in some embodiments, the apparatus is located in an automaticwashing system selected from the group consisting of an automatic warewashing or dish washing machine, automatic vehicle washing system, aninstrument washer, clean in place system, food processing cleaningsystem, bottle washer, an automatic laundry washing machine, andcombinations thereof. The apparatus can be located upstream from thewater line feeding a washing machine in some embodiments.

In other aspects, the present invention relates to a method of treatinga water source. The method includes contacting the water source with acatalyst. The catalyst comprises a water treatment agent bound to asupporting material, wherein the water treatment agent is selected fromthe group consisting of a source of magnesium ions, aluminum ions, zincions, titanium ions and mixtures thereof, such that the water istreated. In some embodiments, the treated water has a substantiallyreduced solubilized water hardness. In some embodiments, the step ofcontacting can include passing the water source through the catalyst.

In other aspects, the present invention relates to methods of using atreated water source to clean an article. The method comprises treatinga water source with a catalyst. The catalyst comprises a water treatmentagent bound to a supporting material, wherein the water treatment agentis selected from the group consisting of a source of magnesium ions,aluminum ions, zinc ions, titanium ions and mixtures thereof. A usesolution is formed with the treated water and a detergent; andcontacting the article with the use solution such that the article iscleaned.

In still yet other aspects, the present invention relates to methods fortreating a food processing stream. The method comprises contacting thefood processing stream with a catalyst. The catalyst comprises a watertreatment agent bound to a supporting material, wherein the watertreatment agent comprises a source of magnesium ions, such that the foodprocessing stream is treated.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of an apparatus for use in treating wateraccording to embodiments of the invention.

FIG. 2 is a photograph of test glasses washed in water which was treatedto reduce solubilized water harness according to embodiments of theinvention.

FIG. 3A is a photograph of test glasses washed in detergent withoutbuilders and rinse aids with untreated water.

FIG. 3B is a photograph of test glasses washed in detergent with outbuilders and rinse aids and with water treated to reduce solubilizedwater hardness according to embodiments of the invention.

FIG. 3C is a photograph of test glasses washed in detergent withbuilders and rinse aids and with untreated water.

FIG. 3D is a photograph of test glasses washed in detergent withbuilders and rinse aids and with water treated to reduce solubilizedwater hardness according to embodiments of the invention.

FIGS. 4A and 4B are photographs of test glasses washed with untreatedwater, water treated with a calcium bound resin, water treated with amagnesium bound resin, and water treated with a hydrogen bound resin.

DESCRIPTION

The present invention relates to apparatuses and methods for treatingwater, such that the solubilized water hardness is controlled and/orreduced. In some embodiments, the solubilized calcium portion of waterhardness is reduced. In some aspects, a water treatment agent is boundto a resin and is used to treat the water. In some embodiments, thewater treatment agent is magnesium and the resin is a weak acid cationresin.

The water treated in accordance with the methods of the presentinvention has many beneficial effects, including, but not limited to,reduction of scale and soiling in areas where hard water can causesoiling, protecting equipment, e.g., industrial equipment, from scalebuild up, increased cleaning efficacy when used with conventionaldetersive compositions, and reducing the need for specific chemistries,e.g., those containing threshold agents, chelating agents, orsequestrants, or phosphorous, in downstream cleaning processes.

In some aspects, the present invention provides methods for treatingwater. In some embodiments, the solubilized calcium portion of waterhardness is reduced. In some embodiments, the water is contacted with acatalyst including a water treatment agent. In other aspects, thepresent invention provides methods for inhibiting or reducing scaleformation in an aqueous system including contacting the aqueous systemwith a catalyst including one or more water treatment agents bound to asupport material and/or one or more unbound conversion agents.

So that the invention may be more readily understood certain terms arefirst defined.

As used herein, the terms “builder,” “chelating agent,” and“sequestrant” refer to a compound that forms a complex (soluble or not)with water hardness ions (from the wash water, soil and substrates beingwashed) in a specific molar ratio. Chelating agents that can form awater soluble complex include sodium tripolyphosphate, EDTA, DTPA, NTA,citrate, and the like. Sequestrants that can form an insoluble complexinclude sodium triphosphate, zeolite A, and the like. As used herein,the terms “builder,” “chelating agent,” and “sequestrant” aresynonymous.

As used herein, the term “free of chelating agent” or “substantiallyfree of chelating agent” refers to a composition, mixture, oringredients that does not contain a chelating agent, builder, orsequestrant or to which only a limited amount of a chelating agent,builder, or sequestrant has been added. Should a chelating agent,builder, or sequestrant be present, the amount of a chelating agent,builder, or sequestrant shall be less than about 7 wt %. In someembodiments, such an amount of a chelating agent, builder, orsequestrant is less than about 2 wt %, less then about 0.5 wt %, or lessthan about 0.1 wt %.

As used herein, the term “lacking an effective amount of chelatingagent” refers to a composition, mixture, or ingredients that containstoo little chelating agent, builder, or sequestrant to measurably affectthe hardness of water.

As used herein, the term “solubilized water hardness” refers to hardnessminerals dissolved in ionic form in an aqueous system or source, i.e.,Ca⁺⁺ and Mg⁺⁺. Solubilized water hardness does not refer to hardnessions when they are in a precipitated state, i.e., when the solubilitylimit of the various compounds of calcium and magnesium in water isexceeded and those compounds precipitate as various salts such as, forexample, calcium carbonate and magnesium carbonate.

As used herein, the term “water soluble” refers to a compound that canbe dissolved in water at a concentration of more than 1 wt-%.

As used herein, the terms “slightly soluble” or “slightly water soluble”refer to a compound that can be dissolved in water only to aconcentration of 0.1 to 1.0 wt-%.

As used herein, the term “substantially water insoluble” or “waterinsoluble” refers to a compound that can be dissolved in water only to aconcentration of less than 0.1 wt-%. For example, magnesium oxide isconsidered to be insoluble as it has a water solubility (wt %) of about0.00062 in cold water, and about 0.00860 in hot water. Other insolublecompounds for use with the methods of the present invention include, forexample: magnesium hydroxide with a water solubility of 0.00090 in coldwater and 0.00400 in hot water; aragonite with a water solubility of0.00153 in cold water and 0.00190 in hot water; and calcite with a watersolubility of 0.00140 in cold water and 0.00180 in hot water.

As used herein, the term “threshold agent” refers to a compound thatinhibits crystallization of water hardness ions from solution, but thatneed not form a specific complex with the water hardness ion. Thisdistinguishes a threshold agent from a chelating agent or sequestrant.Threshold agents include a polyacrylate, a polymethacrylate, anolefin/maleic copolymer, and the like.

As used herein, the term “free of threshold agent” or “substantiallyfree of threshold agent” refers to a composition, mixture, or ingredientthat does not contain a threshold agent or to which only a limitedamount of a threshold agent has been added. Should a threshold agent bepresent, the amount of a threshold agent shall be less than about 7 wt%. In some embodiments, such an amount of a threshold agent is less thanabout 2 wt-%. In other embodiments, such an amount of a threshold agentis less then about 0.5 wt-%. In still yet other embodiments, such anamount of a threshold agent is less than about 0.1 wt-%.

As used herein, the term “antiredeposition agent” refers to a compoundthat helps keep a soil composition suspended in water instead ofredepositing onto the object being cleaned.

As used herein, the term “phosphate-free” or “substantiallyphosphate-free” refers to a composition, mixture, or ingredient thatdoes not contain a phosphate or phosphate-containing compound or towhich a phosphate or phosphate-containing compound has not been added.Should a phosphate or phosphate-containing compound be present throughcontamination of a phosphate-free composition, mixture, or ingredients,the amount of phosphate shall be less than about 1.0 wt %. In someembodiments, the amount of phosphate is less than about 0.5 wt %. Inother embodiments, the amount of phosphate is less then about 0.1 wt %.In still yet other embodiments, the amount of phosphate is less thanabout 0.01 wt %.

As used herein, the term “phosphorus-free” or “substantiallyphosphorus-free” refers to a composition, mixture, or ingredient thatdoes not contain phosphorus or a phosphorus-containing compound or towhich phosphorus or a phosphorus-containing compound has not been added.Should phosphorus or a phosphorus-containing compound be present throughcontamination of a phosphorus-free composition, mixture, or ingredients,the amount of phosphorus shall be less than about 1.0 wt %. In someembodiments, the amount of phosphorous is less than about 0.5 wt %. Inother embodiments, the amount of phosphorus is less than about 0.1 wt %.In still yet other embodiments, the amount of phosphorus is less thanabout 0.01 wt %.

“Cleaning” means to perform or aid in soil removal, bleaching, microbialpopulation reduction, or combination thereof.

As used herein, the term “ware” refers to items such as eating andcooking utensils and dishes and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware.

As used herein, the term “hard surface” includes showers, sinks,toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, floors, and the like.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of autoclaves andsterilizers, of electronic apparatus employed for monitoring patienthealth, and of floors, walls, or fixtures of structures in which healthcare occurs. Health care surfaces are found in hospital, surgical,infirmity, birthing, mortuary, and clinical diagnosis rooms. Thesesurfaces can be those typified as “hard surfaces” (such as walls,floors, bed-pans, etc.,), or fabric surfaces, e.g., knit, woven, andnon-woven surfaces (such as surgical garments, draperies, bed linens,bandages, etc.,), or patient-care equipment (such as respirators,diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.,),or surgical and diagnostic equipment. Health care surfaces includearticles and surfaces employed in animal health care.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning using watertreated according to the methods of the present invention.

As used herein, the phrases “medical instrument,” “dental instrument,”“medical device,” “dental device,” “medical equipment,” or “dentalequipment” refer to instruments, devices, tools, appliances, apparatus,and equipment used in medicine or dentistry. Such instruments, devices,and equipment can be cold sterilized, soaked or washed and then heatsterilized, or otherwise benefit from cleaning using water treatedaccording to the present invention. These various instruments, devicesand equipment include, but are not limited to: diagnostic instruments,trays, pans, holders, racks, forceps, scissors, shears, saws (e.g. bonesaws and their blades), hemostats, knives, chisels, rongeurs, files,nippers, drills, drill bits, rasps, burrs, spreaders, breakers,elevators, clamps, needle holders, carriers, clips, hooks, gouges,curettes, retractors, straightener, punches, extractors, scoops,keratomes, spatulas, expressors, trocars, dilators, cages, glassware,tubing, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes,stethoscopes, and arthoscopes) and related equipment, and the like, orcombinations thereof.

As used herein, the term “laundry,” refers to woven and non-wovenfabrics, and textiles. For example, laundry can include, but is notlimited to, clothing, bedding, towels and the like.

As used herein, the term “water source,” refers to any source of waterthat can be used with the methods, systems and apparatus of the presentinvention. Exemplary water sources suitable for use in the presentinvention include, but are not limited to, water from a municipal watersource, or private water system, e.g., a public water supply or a well.The water can be city water, well water, water supplied by a municipalwater system, water supplied by a private water system, and/or waterdirectly from the system or well. The water can also include water froma used water reservoir, such as a recycle reservoir used for storage ofrecycled water, a storage tank, or any combination thereof. In someembodiments, the water source is not an industrial process water, e.g.,water produced from a bitumen recovery operation. In other embodiments,the water source is not a waste water stream.

The methods, systems, apparatuses, and compositions of the presentinvention can include, consist essentially of, or consist of thecomponents and ingredients of the present invention as well as otheringredients described herein. As used herein, “consisting essentiallyof” means that the methods, systems, apparatuses and compositions mayinclude additional steps, components or ingredients, but only if theadditional steps, components or ingredients do not materially alter thebasic and novel characteristics of the claimed methods, systems,apparatuses, and compositions.

As used herein, “weight percent,” “wt-%,” “percent by weight,” “% byweight,” and variations thereof refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

As used herein, the term “about” or “approximately” refers to variationin the numerical quantity that can occur, for example, through typicalmeasuring and liquid handling procedures used for making concentrates oruse solutions in the real world; through inadvertent error in theseprocedures; through differences in the manufacture, source, or purity ofthe ingredients used to make the compositions or carry out the methods;and the like. The term “about” also encompasses amounts that differ dueto different equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes acomposition having two or more compounds. It should also be noted thatthe term “or” is generally employed in its sense including “and/or”unless the content clearly dictates otherwise.

Water Hardness/Water Sources

In some aspects, the apparatuses and methods of the present inventionare used to treat a water source such that the solubilized waterhardness in the water source is controlled and/or reduced. The watersource treated may be any source of water having a hardness that wouldbe benefited by treatment in accordance with the methods of the presentinvention. Exemplary water sources suitable for treatment using themethods of the present invention include, but are not limited to,ordinary tap water such as water from a municipal water source, orprivate water system, e.g., a public water supply or a well. The watercan be city water, well water, water supplied by a municipal watersystem, water supplied by a private water system, and/or water directlyfrom the system or well. In some embodiments, the water source is not anindustrial process water, e.g., water produced from a bitumen recoveryoperation. In other embodiments, the water source is not a waste waterstream.

The apparatus, systems and methods of the present invention includetreating a water source such that the solubilized hardness of the wateris controlled. In some aspects, the solubilized hardness of the water isreduced. In some aspects, the present invention provides methods forreducing or inhibiting scale formation in an aqueous system.

In some embodiments, an aqueous system, i.e., a water source, iscontacted with one or more water treatment agents bound to a resinand/or unbound conversion agents. Without wishing to be bound by anyparticular theory, it is thought that the water treatment agents causesolubilized calcium water hardness ions in water to substantiallyprecipitate via an interfacial reaction from solution as calciumcarbonate in the thermodynamically unfavorable crystal form aragoniterather than as the thermodynamically favorable crystal form calcite.Aragonite is a fragile crystal which doesn't bind well to surfaces anddoesn't form hard water scale while calcite is a more robust crystalwhich binds tightly to surfaces, forming a hard water scale that's notseen with aragonite. Thus, contacting water with a water treatment agentof the present invention reduces the solubilized water hardness of thetreated water, and leads to a reduction in scale formation on a surfacein contact with the treated water. The aragonite crystals can also actas seed crystals for further reduction of solubilized calcium aftercontacting the water treatment agent.

The methods of the present invention are especially effective atremoving or preventing scale formation wherein the scale includescalcium salts, e.g., calcium phosphate, calcium oxalate, calciumcarbonate, calcium bicarbonate or calcium silicate. The scale which isintended to be prevented or removed by the present invention may beformed by any combination of the above-noted ions. For example, thescale may involve a combination of calcium carbonate and calciumbicarbonate.

In some embodiments the water source has a pH of between about 6 andabout 11 prior to treatment using the methods, apparatuses, or systemsof the present invention. In some embodiments, the pH of the watersource prior to treatment is greater than about 8. In some embodiments,the pH of the water source is raised to greater than 9, and in someembodiments the pH is greater than 10 prior to treatment. In someembodiments, the pH of the water source is increased prior to contactingthe catalysts, such as by injecting an alkaline chemical into thefeedstream or by applying a self-buffering alkali source, such as MgO orcalcite, to the water source. In some embodiments, the water source hasa pH greater than about 9 prior to treatment with the catalyst and theprecipitate does not need to be filtered because the formation of largeflocculent forms of precipitant is avoided. For example, more than 200ppm sodium carbonate (e.g., up to about 5,000 ppm) may be added to thetreated water source, raising the pH above about 10, and the treatedwater would not need to be filtered.

Catalyst

Embodiments of the invention include a catalyst including a supportmedium and a water treatment agent bound to the support medium. Thewater treatment agent may be ionically bound or physically bound to thesupport medium. The catalyst may be contained within a treatmentreservoir. In some embodiments, the catalyst includes an additionalfunctional ingredient which is not bound to a support medium. In furtherembodiments, the catalyst includes one or more water treatment agentsbound to a support medium and one or more additional functionalingredients which are not bound to a support medium.

As used herein, the term “water treatment agent” refers to a speciesthat causes solubilized calcium in water to substantially precipitatefrom solution as calcium carbonate in a form which is thought to be thethermodynamically unfavorable crystal form aragonite rather than as thethermodynamically favorable crystal form calcite. Aragonite is a fragilecrystal which doesn't bind well to surfaces and doesn't form hard waterscale while calcite is a more robust crystal which binds tightly tosurfaces, forming a hard water scale that's not seen with aragonite.

Water treatment agents suitable for use with the methods and apparatusof the present invention include sources of magnesium ions, iron ions,aluminum ions, titanium ions, and zinc ions and polymorphs of calcium.In some embodiments, the water treatment agents suitable for use withthe methods and apparatus of the present invention do not includealuminum, zinc and/or titanium ions. One or more water treatment agentsmay be used. In some embodiments, the water treatment agent is selectedfrom the group consisting of sources of magnesium, aluminum, andtitanium ions and polymorphs of calcium. In some embodiments, the watertreatment agent includes only a source of magnesium ions.

While not intending to be bound by theory, it is believed that the watertreatment agents act as catalyst by acting as nucleation seeds toprecipitate calcium carbonate out of the water in the form of aragonite.As such, the water treatment agent does not undergo an ionic exchangewhich would require recharging of the resin with new water treatmentagent, as in existing water treatment systems. Rather, the watertreatment agent remains adjoined to the catalyst and continues topromote the precipitation of calcium carbonate over an extended periodof time without needing to be replaced for a long time. As aragoniteprecipitates on the surface of the resin system it promotes furtherprecipitation of aragonite. As the resin column is agitated some of thearagonite crystals are broken off the surface of the resin system andmixed back into the water as precipitated seed crystals. This processreaches a steady state so the rate of crystallization equals the rate ofremoval from the surface.

Ongoing experiments have shown that the catalyst continues to functionafter treating 25,000 gallons of water per pound of resin without fail.In practice, the lifespan of the catalyst will depend upon the waterconditions and the presence of contaminants in the water. In averagewater conditions, the catalyst may last 1 or 2 years, while in very goodwater conditions or in low water usage rates it may last 5 or 10 years.In some embodiments, water contacted with a water treatment agent formsa precipitate which includes a cation which is different from the watertreatment agent. For example, in some embodiments the water treatmentagent includes a source of magnesium ions and the precipitate formedincludes calcium. In some embodiments, water contacted with a watertreatment agent forms a calcium precipitate. The calcium precipitateformed using the methods of the present invention is such that theprecipitate (e.g. aragonite crystals) flows through the water sourceharmlessly. That is, in some embodiments, unlike conventional watertreatment systems, there is not a need to filter or remove theprecipitate from the treated water.

The catalyst can further include additional functional ingredients.Additional functional ingredients suitable for use with the methods ofthe present invention include any materials that impart beneficialproperties to the catalyst, the water source being treated, or anycombination thereof. For example, functional ingredients may be addedthat aid in the prevention of “cementing” of the catalyst, i.e.,agglomeration of the particles, as it is contacted with a water source.

In some embodiments, the catalysts of the present invention furtherinclude one or more additional functional ingredients including, but notlimited to, metal oxides, metal hydroxides, polymorphs of calciumcarbonate (non-Calcite forms) and combinations and mixtures thereof. Insome embodiments, the additional ingredient includes one or more metaloxide, such as magnesium oxide, aluminum oxide, and titanium oxide, forexample. In some embodiments, the additional functional ingredientincludes one or more metal hydroxide, such as magnesium hydroxide,aluminum hydroxide, and titanium hydroxide, for example. Polymorphs ofcalcium carbonate such as aragonite may also be used in embodiments ofthe invention.

In some embodiments, the additional functional ingredient used includesa metal oxide and a metal hydroxide in combination, such as magnesiumoxide and magnesium hydroxide. The additional ingredients may be in anyform, e.g., solid, particle, liquid, powder, nanoparticle, slurry,suitable for use with the methods of the present invention. In someembodiments, a solid source of an additional functional ingredient isused.

In some embodiments, the catalyst includes a combination of a watertreatment agent bound to a support medium and an unbound additionalfunctional ingredient. For example, in one embodiment, the catalystincludes magnesium bound to a support medium as well as unboundadditional ingredient such as magnesium oxide and/or magnesiumhydroxide. In some embodiments, the bound water treatment agent andunbound additional ingredient are physically present together, such asmixed together in the same treatment reservoir or as separate layers inthe same treatment reservoir. In other embodiments, the bound watertreatment agent and the unbound additional ingredient are separate, suchas in different treatment reservoirs operating in series.

In some embodiments, the additional functional ingredient includes amixed cation compound of calcium and magnesium ions. In someembodiments, the additional functional material includes calciummagnesium carbonate, some natural minerals of which may also be known bythe name dolomite. In some embodiments, one or more additionalfunctional ingredients are bound to the supporting material.

Supporting Material

In some aspects, the catalysts for use with the present inventioninclude a supporting material. The supporting material may be anymaterial to which a water treatment agent can be bound. In someembodiments, the catalysts includes more than one different supportingmaterial.

In some embodiments, the supporting material has a density slightlyhigher than the density of water to maximize fluidization and/oragitation of the supporting material. In some embodiments, thesupporting material binds cations by ionic or electrostatic force. Insome embodiments, the bound cation is magnesium. In some embodiments,the supporting material is inert.

In some embodiments, the water treatment agent includes a resin. In someembodiments, the supporting material is a resin capable of bindingmagnesium ions preferentially over binding calcium ions. The resin foruse as a supporting material can include any ion exchange resin. Forexample, in some embodiments, the resin includes an acid cation exchangeresin, e.g., a weak acid cation exchange resin, or a strong acid cationexchange resin. In other embodiments, the supporting material is achelating resin.

In some embodiments, the resin includes an acrylic acid polymer ormethacrylic acid polymer. In some embodiments, the supporting materialis not inorganic. In some embodiments, the supporting material comprisesa polymer having sulfonic acid substituents. For example, in someembodiments, the supporting material does not include a ceramicmaterial, and/or zeolites.

The supporting material may be provided in any shape and size, includingbeads, sheets, rods, disks or combinations of more than one shape.

The water treatment agent may be bound to the support material in avariety of ways. For example, the resin may be loaded with the magnesiumresin by an ion exchange mechanism. In a two-step process, the hydrogenon an acid resin is first exchanged with sodium and then finallyexchanged with the final cation using the salt of the water treatmentagent. For example, in some embodiments, a magnesium bound resincatalyst may be created from a weak acid cation exchange resin having aH+ ion attached to the active sites, such as carboxylic acid groups. Theweak acid cation exchange resin can be first converted to a sodium form,such as by soaking the resin in an excess of sodium hydroxide for 4 to12 hours and then rinsing with water, and then the sodium form may beconverted to a magnesium form, such as by using soluble magnesium salts,such as MgCl₂ and MgSO₄, for example.

Alternatively, the water treatment agent may be bound to the supportingmaterial using a one-step process. In some embodiments, the magnesiummay be directly exchanged with the hydrogen on the surface of an acidresin. For example, the resin may be soaked in an excess of magnesiumsalt, such as MgCl₂ or MgSO₄, for a sufficient time such as 4 to 12hours, and then rinsed with water. Soluble magnesium salts which may beused include magnesium chloride, magnesium sulfate, for example. Inother embodiments, the weak acid cation exchange resin may be convertedto a magnesium form using a low solubility magnesium source, such asmagnesium hydroxide, magnesium oxide, for example. For example, MgO canbe added to an apparatus containing a resin and either mixed with theresin, or used as a separate pre-conditioning stage of the apparatus. Insome embodiments, magnesium is bound to the supporting material usingthe one-step process using MgO or MgOH, and some residual MgO or MgOHremain on the surface where they may enhance the water treatmentactivity of the catalyst.

In other embodiments, the resin includes a weak acid cation exchangeresin having H+ ions attached to the active sites. The resin may then beneutralized by having a water source run over it. Without wishing to bebound by any particular theory, it is thought that as the water runsover the resin, the calcium and magnesium ions in the water will attachto the resin, thereby neutralizing it.

Similar two step or one step processes could be used to bind other watertreatment agents such as aluminum, titanium, zinc, and polymorphs ofcalcium, to the supporting material.

In some embodiments, a layer of a magnesium source may be providedbeneath an un-neutralized resin in a treatment reservoir, so that whenwater flows through the reservoir, the catalyst is converted to themagnesium form. For example, the reservoir is first filled with themagnesium source (soluble or insoluble). The un-neutralized resin isadded on top of the magnesium source. When the water starts to flowthough the reservoir from the bottom up, it picks up some of themagnesium and this material will react with the resin to form thesupported catalyst resin system.

The water treatment agent may be ionically or physically bound to thesupporting medium. For example, in some embodiments, Ca2+ or Mg2+ have aloose ionic bond with a weak acid resin substrate, providing a largeamount of active surface area as the ions are held loosely in there inionic form and catalyzing the precipitation of aragonite.

Treatment Reservoir

Embodiments of the invention include one or more treatment reservoirswhich contains the catalyst. Embodiments of the invention include asystem or apparatus having a single treatment reservoir, one or moretreatment reservoirs in parallel and/or one or more treatment reservoirsin series. In embodiments which include more than one treatmentreservoir, each treatment reservoir may include the same one or morecatalysts or may include different one or more catalysts. For example,the water source may be passed over a plurality of reservoirs, in thesame or in separate vessels, including the same or different catalysis,i.e. water treatment agents bound to a supporting material.

The treatment reservoir may be any shape or size appropriate for the useof the water and the volume of water to be treated. In some embodiments,the apparatus includes a vessel which includes a treatment reservoir.The treatment reservoir may be for example, a tank, a cartridge, afilter bed of various physical shapes or sizes, or a column. In someembodiments, the treatment reservoir is pressurized. In otherembodiments, the treatment reservoir is not pressurized.

Some embodiments of the invention include a treatment reservoirincluding a water inlet and a water outlet. In some embodiments, thewater may enter and exit the treatment reservoir through the sameopening or channel. In some embodiments, the treatment reservoir iscontained within a vessel. Water to be treated enters the vessel throughan inlet located at or near the top of a vessel, flows downward alongthe vessel wall or walls, and enters the treatment reservoir at thebottom of the vessel. The water flows upward through the treatmentreservoir toward the top of the vessel and exits the vessel through anoutlet at or near the top of the vessel.

An example of a system for treating water according to embodiments ofthe invention is shown in FIG. 1, a schematic of an apparatus of thepresent invention is shown at reference 10. The apparatus includes: aninlet 12 for providing the water source to a treatment reservoir 14; atreatment reservoir 14 including a water treatment agent 16; an outlet18 for providing treated water from the treatment reservoir; and atreated water delivery line 20. In some embodiments, the treated waterdelivery line 20 provides water to a selected cleaning device. In someembodiments, there is no filter between the outlet and the treated waterdelivery line. A flow control device 22 such as a valve 24 can beprovided in the treated water delivery line 20 to control the flow ofthe treated water into the selected end use device, e.g., a warewashingmachine, a laundry washing machine.

In some embodiments, the entire treatment reservoir can be removable andreplaceable. In other embodiments, the treatment reservoir can beconfigured such that catalyst contained within the treatment reservoiris removable and replaceable. In some embodiments, the treatmentreservoir includes a removable, portable, exchangeable cartridgeincluding a water treatment agent, e.g., magnesium, bound to asupporting material, such as a weak acid resin.

In some aspects, the present invention provides methods for reducing orcontrolling solubilized water hardness and/or reducing scale formationincluding contacting a water source with a catalyst including a watertreatment agent. The step of contacting can include, but is not limitedto, running the water source over or through a solid source, e.g., acolumn, cartridge, or tank, including the water treatment agent. Thecontact time is dependent on a variety of factors, including, forexample, the pH of the water source, the hardness of the water source,and the temperature of the water source.

In some embodiments, the catalyst is in the form of an agitated bed orcolumn. The bed or column can be agitated by any known method including,for example, by the flow of water through the column, fluidization,mechanical agitation or mixing, high flow backwash, recirculation, airsparge, eductor flow, and combinations thereof. In some embodiments, thecatalyst includes a fluidized bed, e.g., a column or a cartridge, in thetreatment reservoir. Fluidization is obtained by an increase in thevelocity of the fluid, e.g., water, passing through the bed such that itis in excess of the minimum fluidization velocity of the media.

As the catalyst promotes precipitation of the calcium carbonate, thecalcium carbonate may be bound to the catalyst. Therefore, the catalyst,such as the bed or column may be agitated to avoid “cementing,” i.e.,agglomeration of the catalyst once contacted with the water source. Suchagitation may prevent the precipitant from binding to the catalystand/or may cause precipitated calcium to become dislodged from thecatalyst. For example, as the aragonite precipitates on a catalyst,agitation of the catalyst results the beads or granules of the supportmedia, for example, to bounce into each other and/or to bound into thesolid unbound conversion agent. The physical impact knocks off theprecipitate, such as aragonite crystals. The loose calcium carbonatecrystals may then pass through and exit the treatment reservoir alongwith the treated water. In this way, the agitation of the catalystcauses it to be self-cleaning, exposing the catalyst and enabling it tocontinue nucleating and precipitating the calcium carbonate from thewater source. It has been discovered that the catalyst according toembodiments of the invention can continue to perform excellently on veryhard water, such as 17 grain water, even after used to treat water for900 consecutive dishmachine cycles, with the inside of the dishmachineremaining nearly perfect, whereas untreated was resulted in heavy scaledeposits.

The crystals are very small in size, are inert and non-reactive, and donot stick to surfaces. For example, aragonite crystals formed accordingto embodiments of the invention may be between approximately 10 nm and1000 nm in size. Because it is inert and small in size, the precipitatedcalcium carbonate does not need to be filtered or removed from thetreated water. Rather, the treated water containing the precipitatedcrystals of calcium carbonate can be used for any downstreamapplication.

The treatment reservoir may be contained in a vessel which can be small,such as a canister filter-type vessel as used for small drinkingpurification processes. Alternatively, the vessel can be large, such asa large water treatment tank as used in whole house water softening.

As water passes through the treatment reservoir, the water treatmentagent bound resin treats the water by nucleating and precipitatingcalcium carbonate out of the water. In some embodiments, the flow ofwater is in the upward direction. For example, in some embodiments, thewater enters the treatment reservoir through an inlet in a bottomportion of the reservoir, flows up through the catalyst, and exits thetreatment reservoir through an outlet at a top portion of the treatmentreservoir.

The treatment reservoir may be sized and shaped to increase theagitation and fluidization of the catalyst as water contacts it. Theagitation works to keep the catalyst clean from precipitated calciumcarbonate. In some embodiments, the volume of the vessel is minimized,such that it contains only enough water for the application or intendeduse such that the residence time is not excessively low. This designprevents the water in the reservoir from getting stagnant and reducesthe possible risk of bulk precipitation and accumulation of calciumcarbonate in the reservoir. In some embodiments, the volume of water inthe vessel may be completely evacuated with each use of the water. Insome embodiments, the vessel is sized such that there is sufficienthead-space (or free-board) above the resin to permit the resin to riseand be agitated as water passes through. In some embodiments, thefree-board space is equal to approximately 100% of the volume of thecatalyst.

In some embodiments, the catalyst is agitated using fluidization forcesto create a flowing bed that is in constant agitation when the water isflowing. In other embodiments, the catalyst is agitated usingcentrifugal forces created by tangential water flows, mechanicalagitation, or ultrasound agitation, for example. The agitationultimately results in a cleaning of the catalysts, removing the calciumcrystals from the catalysts, such that water can continue to flow overor through the media with reduced obstruction.

Methods of Use

The methods, apparatuses, and systems of the invention may be used for avariety of purposes. For example, an apparatus for employing the watertreatment methods of the present invention can be connected to the watermain of a house or business. The apparatus can be employed in linebefore the hot water heater, or after the hot water heater. Thus, anapparatus of the present invention can be used to reduce solubilizedwater hardness in hot, cold and room temperature water sources. In someembodiments, the water to be treated in accordance with the presentinvention is at a temperature of between about 10° C. and about 90°. Insome embodiments, the temperature of the water to be treated is aboveroom temperature, e.g., greater than about 20° C.

In some aspects, the present invention provides a system for use in acleaning process. The system includes providing a water source to anapparatus for treating the water source. In some embodiments, theapparatus for treating the water source includes: (i) an inlet forproviding the water source to a treatment reservoir; (ii) a treatmentreservoir containing a catalyst including a water treatment agent boundto a supporting media and/or an unbound additional functionalingredient; (iii) an outlet for providing treated water from thetreatment reservoir; and (iv) a treated water delivery line forproviding the treated water to the automatic washing machine, such as awarewashing machine. In some embodiments, a device, e.g., a screen, ispresent in the treatment reservoir in order to keep the water treatmentagent contained within the treatment reservoir as the fluid is passingover or through it. In some embodiments, the apparatus is filterless,with no filter between the outlet and the treated water delivery line.

Once the water has been treated, the treated water is provided to anautomatic washing machine, e.g., an automatic ware washing ordishwashing machine, a vehicle washing system, an instrument washer, aclean in place system, a food processing cleaning system, a bottlewasher, and an automatic laundry washing machine, from the treated waterdelivery line of the apparatus. Alternatively, the treated water may beused in a manual washing system. Any automatic or manual washing machinethat would benefit from the use of water treated in accordance with themethods of the present invention can be used. The treated water is thencombined with a detersive composition in the washing machine to providea use composition. Any detersive composition can be used in the systemof the present invention, for example, a cleaning composition, a rinseagent composition or a drying agent composition. The articles to becleaned are then contacted with the use solution in the automaticwashing machine such that they are cleaned.

The water treatment methods and systems of the present invention can beused in a variety of industrial and domestic applications. The watertreatment methods and systems can be employed in a residential settingor in a commercial setting, e.g., in a restaurant, hotel, hospital. Forexample, a water treatment method, system, or apparatus of the presentinvention can be used in: ware washing applications, e.g., washingeating and cooking utensils and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, and floors; inlaundry applications, e.g., to treat water used in an automatic textilewashing machine at the pre-treatment, washing, souring, softening,and/or rinsing stages; in vehicle care applications, e.g., to treatwater used for pre-rinsing, e.g., an alkaline presoak and/or low pHpresoak, washing, polishing, and rinsing a vehicle; industrialapplications, e.g., cooling towers, boilers, industrial equipmentincluding heat exchangers; in food service applications, e.g., to treatwater lines for coffee and tea brewers, espresso machines, ice machines,pasta cookers, water heaters, steamers and/or proofers; in healthcareinstrument care applications, e.g., soaking, cleaning, and/or rinsingsurgical instruments, treating feedwater to autoclave sterilizers; andin feedwater for various applications such as humidifiers, hot tubs, andswimming pools

In some embodiments, the water treatment methods and systems of thepresent invention can be applied at the point of use. That is, a watertreatment method, system, or apparatus of the present invention can beapplied to a water source upstream of an application such as a washingsystem. In some embodiments, the water treatment is applied immediatelyprior to the desired end use of the water source. For example, anapparatus of the present invention could be employed to a water lineconnected to a household or restaurant appliance, e.g., a coffee maker,an espresso machine, an ice machine. An apparatus employing the methodsof the present invention may be located in a washing system. Forexample, it can also be included as part of an appliance which uses awater source, e.g., a water treatment system built into an automatic ormanual washing system, a coffee maker, an ice machine, or any othersystem which may benefit from the use of treated water.

A treatment reservoir according to embodiments of the invention may beused with a washing machine in a variety of ways. In some embodiments,the treatment reservoir may be connected to a detergent dispensingdevice. The treatment reservoir may be used to supply treated water to awashing system and/or to a rinsing system of a washing machine. In someembodiments, the treatment reservoir may be used to supply a mixture oftreated water and detergent to a washing system.

Additionally, an apparatus for employing the water treatment methods ofthe present invention can be connected to the water main of a house orbusiness. The apparatus can be employed in line before the hot waterheater, or after the hot water heater. Thus, an apparatus of the presentinvention can be used to reduce solubilized water hardness in hot, coldand room temperature water sources.

Because the embodiments of the invention are so useful at removingsolubilized hardness from water, treated water may be used withdetergents having reduced amounts of builders or that are low inbuilders. In some embodiments, the treated water may be used withdetergents which are substantially free of builders. In someembodiments, the treated water may be used with detergents which aresubstantially free of chelant, builder, threshold agent, sequestrant orcombinations thereof. Besides being economically advantageous, the useof low builder detergents or no builder detergents allowed byembodiments of the invention is also more beneficial to the environment,as is the elimination of the need to regenerate the system such as byusing sodium chloride.

The methods, apparatuses, and systems of the present invention may alsobe used in the food and beverage industry, for example in a food andbeverage processing application. In some embodiments, the watertreatment apparatuses can be used upstream from a reverse osmosismembrane (“RO membrane”), a nanofiltration system (“NF system”), or anultrafiltration system (“UF system”) (collectively “RO/NF/UF systems”)or an evaporator in a food or beverage processing application, e.g., anapplication to treat whey permeate.

For example, the methods and apparatuses can be used to prevent calciumscale formation on evaporators and RO/NF/UF systems used to process wheypermeate, or other mineral containing feed streams. Whey permeatecontains water, lactose and minerals, e.g., calcium phosphate. Thepermeate is about 6% lactose and is typically concentrated using ROfiltration to reach about 18% solids. The permeate is furtherconcentrated using an evaporator to reach about 65% solids. RO/NF/UFsystems are known to be fouled by the mineral, resulting in increasedpressure for permeation and/or a decreased flow rate.

During evaporation, the evaporator is fouled by mineral depositsincluding mostly calcium phosphate scale. This scale reduces heattransfer efficiency which in turn requires an increase in steam and/or adecrease in feed flow rate to maintain the finished solids content.Current scale reducing treatments include adding polyphosphates to thefeed stream to minimize scaling, and using large amounts of acid todissolve and remove the scale from the RO/NF/UF units and evaporators.Using the apparatus, systems or methods of the invention upstream froman RO/NF/UF system or an evaporator may minimize the scaling andincrease production efficiency without having to use polyphosphatetreatments or treating the evaporator or RO/NF/UF units with a largeamount of acid to dissolve the scale.

In some embodiments, the methods and apparatus may also be used toproduce and isolate aragonite. Precipitates of aragonite may be removedfrom the water by filtration, for example, and used for industrial orpharmaceutical purposes.

EXAMPLES Example 1

Three resin samples were prepared by loading them with H+, Ca+, and Mg+.The magnesium loaded sample was prepared according to the followingprocedure. A weak acid cation resin, Lewatit S 8528 obtained from theLanxess Company, was soaked in 500 grams of NaOH beads and 2500 ml ofsoftened water for 24 hours. The pH was approximately 12-13. Aftersoaking, the resin was then rinsed thoroughly with softened water threetimes until the pH of the rinse water was below 11. The resin was soakedin 2500 ml of softened water with 700 grams of a MgCl₂.6H₂0 compositionfor 4 days. The resin was thoroughly rinsed with softened water threetimes. The final pH of the rinse water was approximately 7.5-8.5. Toload the resin with Ca++, the same procedure was used as the MG++ resin,only the resin was soaked with CaCl₂ composition. The H+ form of theresin, was the resin itself, without any cations loaded onto it.

The magnesium treated resin produced by this method was used in Examples3-5, below.

Example 2

The following alternative process was used to produce a magnesium formof a weak acid cation exchange resin: Lewatit S 8528 resin was soaked ina 60% magnesium hydroxide slurry for 4 days. The final pH of the rinsewater was 11.0.

Example 3

Two pounds of the magnesium treated resin, produced according to themethod of Example 1, was used to treat 17 gpg (grain per gallon) hardwater. The two pounds of resin was placed into a flow-through reservoirand connected to the inlet of an institutional dishwashing machine. Thetreated water was then used to wash test glasses in an AM-14 automaticware washing machine with no detergent and no rinse-aid. After 1100cycles using the same water treatment reservoir and resin, the interiorof the warewashing machine showed no visible scale.

FIG. 2 shows a picture of 8 test glasses, each washed in a dishmachineusing hard water treated with the magnesium catalyst resin. The firstsix glasses from the left were removed from the dishmachine afterconsecutive 100 cycles of the magnesium treated resin and wash cycles ofthe glass. The sixth glass from the left, after 600 cycles of themagnesium treated media and wash cycles, showed no scale buildup. As canbe seen, there was no scale buildup on the glass even after 600wash/rinse cycles while using the magnesium treated resin. The seventhglass from the left was washed 100 times by the same magnesium treatedresin after 800 cycles, and the eighth glass from the left was washed100 times by the same magnesium treated resin after 900 cycles. As canbe seen, even after 900 cycles, there is no scale buildup, indicatingthat the magnesium resin continued to reduce scaling even after 900cycles.

Example 4

Magnesium treated resin, produced according to the method of Example 1,was used to treat 17 Grain water. The water was treated using aflow-through reservoir connected to a hard water tap. The water was runthrough the reservoir to the drain and thus treated continuously forover 15,000 gallons. After treating 15,803 gallons of water, thereservoir was connected to an automatic ware washing machine (TypeAM-14) for 800 cycles with no detergent or rinse aids. Following the 800cycles, the interior of the ware washing machine demonstrated no visiblescale. As a comparison, untreated 17 Grain water was run through a warewashing machine (type AM-14) for 800 cycles with no detergent or rinseaids. The interior of the ware washing machine showed heavy scale. Thisindicates that the resin bound magnesium continued to significantlyreduce the soluble hardness in the water even after treating 15,803gallons of water.

Example 5

Magnesium treated resin, produced according to the method of Example 1,was used to treat 17 Grain water. The treated water was used in anautomatic ware washing machine with a detergent to wash test glasses.The detergent was formulated with and without builder according to table1:

TABLE 1 Detergent Detergent with builder without builder Raw Material(Approx. Wt. %) (Approx. Wt. %) Alkalinity Source 10% 10%  Builders 14%0.0%   Surfactants  4% 4% Soda Ash 67% 81%  Solvent  2% 2% BleachingAgent  3% 3% 100.0%   100% 

The results of this example are shown in FIGS. 3A-3D. In FIG. 3A, theglasses were washed with the detergent without builder and without watertreatment and show heavy scale. In comparison, in FIG. 3B, the glasseswere washed with the same detergent without builder and with watertreated with magnesium bound resin, produced according to the method ofExample 1. These glasses had less scale and looked better than theglasses washed in the untreated water. This indicates that the use ofthe magnesium bound resin catalyst reduced the need for builder in thedetergent, even in 17 Grain water.

The glasses in FIG. 3C were washed in untreated 17 Grain water using thedetergent including builder, while those in the FIG. 3D were washed inthe same detergent but using treated water as described above withregard to FIG. 3B. The glasses in the FIG. 3C show a slight amount ofscale, while the glasses in FIG. 3D have no scale.

Example 6

Three resin samples were prepared by loading them with H+, Ca++, andMg++, according to the resin loading procedure described in example 1.Water was then treated with each of the resin samples and compared forscaling tendencies in a warewashing machine. The feedwater to thedishmachine was thus treated with a H+ weak acid cation resin, a Ca2+weak acid cation resin, or a Mg2+ weak acid cation resin in threeseparate but equivalent tests. Each of the resin samples were firstconditioned by running hard (17 gpg) water through a flow-throughreservoir to drain. After approximately 1000 gallons of water flow, theresin/reservoir systems were connected to the dishmachine and evaluatedfor scaling tendencies on glassware. The results of this comparison testare shown in FIG. 4A. After this dishmachine/glassware scaling test, theresin samples were further conditioned by running hard water through aflow-through reservoir to drain for an additional 4000 gallons andtherefore each resin had treated a total of about 5000 gallons of water.A second set of dishmachine/glassware scaling tests were then conducted,again without detergent and those results are shown in FIG. 4B.

The control glasses (not shown) had heavy scale. The first two glassesfrom the left in each FIGS. 4A and 4B were treated with H+ bound resin.The third and fourth glass from the left in each figure were treatedwith Ca2+ bound resin, and the fifth and sixth glass from the left ineach figure were treated with a Mg2+ bound resin. As seen in FIG. 4A,the H+ resin and the Mg2+ resin showed no visible scale in the testusing resin that had previously treated 1000 gallons of water. The twoCa2+ resin showed a clearly visible scale. Referring to FIG. 4B, inwhich each of the resin systems had previously treated 5000 gallons ofwater, the H+ resin resulted in a slight scale on the glassware. TheCa2+ resin showed a slightly heavier scale, and the Mg2+ resin showedlittle or no visible scale.

Example 7

An experiment was performed to evaluate the effect of various watertreatment apparatuses on the metal content remaining on a stainlesssteel surface after evaporation of whey permeate. Whey permeatecollected from a dairy plant was used for this experiment. The watertreatment apparatuses tested included resins with varying watertreatment agents contained in a vessel. The following apparatuses weretested:

TABLE 2 Apparatus Number: Type 1 Control - 5 micron filter that holds inresin beads 2 A magnesium loaded weak acid cation resin that hadpreviously treated 17 grain hard water. 3 A protonated weak acid cationresin that had not previously treated any water. 4 A magnesium loadedweak acid cation resin that had not previously treated any water. 5 Aprotonated weak acid cation resin rinsed with approximately 1000milliliters of deionized (DI) water.

For each resin, approximately 500 milliliters of permeate was placed inthe resin container and shaken for about 30 seconds. The solutions wherethen allowed to drain through a resin support filter into a beaker.Then, 100 milliliters of each of the treated permeate was placed inseparate stainless steel beakers. The beakers were then placed in a 190°F. to 195° F. water bath to initiate evaporation. After about 4.5 hours,the solutions turned into a thick syrup like solution which was assumedto be about 60-70% brix (60-70% sugar or other dissolved solids insolution).

The beakers were removed from the water bath and rinsed with DI wateruntil the lactose sugary gel was removed, thereby leaving only mineraldeposits. The beakers were then rinsed with a 2% acid solution todissolve the mineral deposits. The acid used contained phosphoric acid,so the phosphoric acid values of the rinsed beakers were not consideredmeaningful in this experiment. The acid solutions and controls were thensubmitted for Inductively Coupled Plasma (ICP) testing for metalcontent. The tables below show the results of this study.

TABLE 3 Treatment Resin Permeate After After Apparatus Wt. TreatedInitial % Treatment Initial Treatment Number (g) (ml) Brix % Brix pH pHObservations Control - N/A N/A 6.3 N/A 5.43 N/A Clear yellow No solutionFiltration End of test after DI rinse, white mineral deposit remained. 1N/A 500 6.3 6.5 5.43 5.51 Clear yellow solution End of test after DIrinse, white mineral deposit remained 2 250 500 6.3 6.1 5.43 6.40 Clearyellow solution after contact with resin Upon heating, a whiteprecipitate formed immediately End of test after DI rinse, beaker hadslight bluing residue 3 113 500 6.3 5.8 5.43 3.58 Cloudy and acidicafter contact with resin End of test after DI rinse, beaker looked clean4 300 458 6.3 5.3 5.43 9.68 Clear yellow solution after contact withresin During evaporation process, solution turned dark brown End of testafter DI rinse, beaker had slight bluing residue 5 113 500 6.3 5.5 5.433.93 Cloudy and less acidic after contact with resin End of test afterDI rinse, beaker looked clean.

TABLE 4 Treatment Apparatus Ca Mg P Na Number (ppm) (ppm) (ppm) (ppm)Observations 1 609 101 507 514 Typical values for a raw permeate control2 269 553 358 311 pH increased slightly from 5.4 to 6.4 3 310 70.5 476391 pH was much more acidic (3.6) after resin treatment 4 6.05 73.6 3712640 pH after resin was very alkaline at 9.7 and brix dropped about 1% 5287 67.5 436 384 Final pH was still acidic at 3.9. Brix dropped about0.8% after treatment.

As can be seen from the above results, the whey treated with Apparatus2, which contained a magnesium loaded weak acid cation resin, showedsome decrease in the percent brix after treatment. This indicates adecrease in lactose, mineral and/or organic content in the treatedsample.

Further, it was observed that the samples treated with resins containingmagnesium (Apparatuses 2 and 4) had a decreased level of calciumremaining in the beaker. This decrease in calcium may be due to areduced amount of calcium from the permeate.

Overall, it was found that the use of water treatment apparatusesaccording to embodiments of the present invention resulted in areduction in the amount of calcium insoluble salts in this permeateevaporation test.

Other Embodiments

It is to be understood that while the invention has been described inconjunction with the detailed description thereof, the foregoingdescription is intended to illustrate, and not limit the scope of theinvention, which is defined by the scope of the appended claims. Otheraspects, advantages, and modifications are within the scope of thefollowing claims.

In addition, the contents of all patent publications discussed supra areincorporated in their entirety by this reference.

It is to be understood that wherever values and ranges are providedherein, all values and ranges encompassed by these values and ranges,are meant to be encompassed within the scope of the present invention.Moreover, all values that fall within these ranges, as well as the upperor lower limits of a range of values, are also contemplated by thepresent application.

1. An apparatus for treating a water source comprising: an inlet forproviding the water source to a treatment reservoir; one or morecatalysts positioned inside the treatment reservoir, the catalystcomprising a water treatment agent bound to a supporting material,wherein the water treatment agent is selected from the group consistingof a source of magnesium ions, aluminum ions, zinc ions, titanium ionsand mixtures thereof; and an outlet for providing treated water from thereservoir.
 2. The apparatus of claim 1, wherein the supporting materialcomprises an ionic resin.
 3. The apparatus of claim 2, wherein the resincomprises a weak acid cation resin.
 4. The apparatus of claim 1, whereinthe water treatment agent comprises magnesium.
 5. The apparatus of claim1, wherein the supporting material comprises beads of resin.
 6. Theapparatus of claim 1, wherein the catalyst is agitated.
 7. The apparatusof claim 1, wherein the treatment reservoir comprises a removablecartridge.
 8. The apparatus of claim 1, wherein the supporting materialis selected from the group consisting of an acrylic acid polymer, amethacrylic acid polymer, and combinations thereof.
 9. The apparatus ofclaim 1, wherein the supporting material comprises a carboxylic acidpolymer.
 10. The apparatus of claim 1, wherein the water treatment agentis ionically bound to the supporting material.
 11. The apparatus ofclaim 1, wherein the supporting material is a resin that binds magnesiumions preferentially over calcium ions.
 12. The apparatus of claim 1,wherein the treatment reservoir further comprises one or more metaloxides or hydroxides.
 13. The apparatus of claim 12, wherein the metaloxide is selected from magnesium oxides, aluminum oxides, titaniumoxides or mixtures thereof.
 14. The apparatus of claim 1, wherein theapparatus is located in a washing system.
 15. The apparatus of claim 14,wherein the washing system is an automated washing system.
 16. Theapparatus of claim 14, wherein the automated washing system is selectedfrom the group consisting of an automatic ware washing machine,automatic vehicle washing system, an instrument washer, clean in placesystem, food processing cleaning system, bottle washer, an automaticlaundry washing machine, and combinations thereof.
 17. The apparatus ofclaim 1, wherein the apparatus is located upstream on a water linefeeding a washing machine.
 18. The apparatus of claim 17, wherein thewashing machine is an automatic washing machine selected from the groupconsisting of an automatic ware washing machine, automatic vehiclewashing system, instrument washer, clean in place system, foodprocessing cleaning system, bottle washer, an automatic laundry washingmachine, and combinations thereof.
 19. The apparatus of claim 1, whereinthe treated water from the outlet does not need to be filtered prior touse.
 20. A method of treating a water source comprising: contacting thewater source with a catalyst, the catalyst comprising a water treatmentagent bound to a supporting material, wherein the water treatment agentis selected from the group consisting of a source of magnesium ions,aluminum ions, zinc ions, titanium ions and mixtures thereof, such thatthe water is treated.
 21. The method of claim 20, wherein the treatedwater has a substantially reduced solubilized water hardness.
 22. Themethod of claim 20, wherein the step of contacting comprises passing thewater source through the catalyst.
 23. The method of claim 20, furthercomprising agitating the catalyst.
 24. The method of claim 20, whereinthe supporting material is an ionic resin.
 25. The method of claim 24,wherein the supporting material is a weak acid cation resin.
 26. Themethod of claim 20, wherein the water treatment agent comprisesmagnesium.
 27. The method of claim 20, wherein the supporting materialcomprises beads of resin.
 28. The method of claim 20, wherein thesupporting material is selected from the group consisting of an acrylicacid polymer, a methacrylic acid polymer, and combinations thereof. 29.The method of claim 20, wherein the catalyst is contained in a treatmentreservoir.
 30. The method of claim 29, wherein the treatment reservoircomprises a removable cartridge.
 31. The method of claim 20, wherein thewater to be treated is at a temperature of between about 10° C. andabout 90° C.
 32. The method of claim 20, wherein the water to be treatedhas a pH of between about 6 and about
 8. 33. The method of claim 20,wherein the water to be treated has a pH of greater than
 8. 34. Themethod of claim 20, wherein the treated water does not need to befiltered after treatment.
 35. The method of claim 20, wherein thetreated water does not have a substantially reduced water hardness levelafter treatment.
 36. The method of claim 20, wherein the pH of thetreated water is substantially similar to the pH of the water sourceprior to treatment.
 37. The method of claim 20, wherein the catalystfurther comprises one or more oxides or hydroxides of magnesium,aluminum or titanium not bound to the supporting material.
 38. Themethod of claim 20, wherein the water contacted with the catalyst formsa precipitate comprising a cation different than the water treatmentagent.
 39. A method of using a treated water source to clean an article,the method comprising: treating a water source with a catalyst, thecatalyst comprising a water treatment agent bound to a supportingmaterial, wherein the water treatment agent is selected from the groupconsisting of a source of magnesium ions, aluminum ions, zinc ions,titanium ions and mixtures thereof; forming a use solution with thetreated water and a detergent; and contacting the article with the usesolution such that the article is cleaned.
 40. The method of claim 39,wherein the catalyst further comprises one or more oxides or hydroxidesof magnesium, aluminum or titanium.
 41. The method of claim 39, whereinthe detergent is substantially free of a chelant, builder, thresholdagent, sequestrant or combinations thereof.
 42. The method of claim 39,wherein the step of contacting the article with the use solution isperformed in an automatic washing machine selected from the groupconsisting of an automatic ware washing machine, automatic dishwashingvehicle washing system, instrument washer, clean in place system, foodprocessing cleaning system, bottle washer, and an automatic laundrywashing machine.
 43. A method for treating a food processing streamcomprising: contacting the food processing stream with a catalyst, thecatalyst comprising a water treatment agent bound to a supportingmaterial, wherein the water treatment agent comprises a source ofmagnesium ions, such that the food processing stream is treated.
 44. Themethod of claim 43, wherein the supporting material comprises a resin.45. The method of claim 44, wherein the resin comprises a weak acidcation resin.
 46. The method of claim 43, wherein the step of contactingcomprises passing the food processing stream through the catalyst. 47.The method of claim 43, wherein the food processing stream comprises awhey permeate.
 48. The method of claim 43, further comprisingconcentrating the treated food processing stream.
 49. The method ofclaim 48, wherein the step of concentrating the food processing streamis selected from the group consisting of passing the treated foodprocessing stream through a reverse osmosis system, passing the treatedfood processing stream through a nanofiltration system, passing thetreated food processing stream through an ultrafiltration system,passing the treated food processing stream through an evaporator, andcombinations thereof.